CN114011428A - Catalyst for preparing decahydronaphthalene by one-step hydrogenation of naphthalene and preparation method thereof - Google Patents
Catalyst for preparing decahydronaphthalene by one-step hydrogenation of naphthalene and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 105
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 title claims abstract description 92
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 41
- 239000012018 catalyst precursor Substances 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000010000 carbonizing Methods 0.000 abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 239000011593 sulfur Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000002779 inactivation Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 231100000572 poisoning Toxicity 0.000 abstract description 2
- 230000000607 poisoning effect Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 28
- 229910052799 carbon Inorganic materials 0.000 description 10
- 239000011280 coal tar Substances 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- 229910020515 Co—W Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910003178 Mo2C Inorganic materials 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- POPHMOPNVVKGRW-UHFFFAOYSA-N 1,2,3,4,4a,5,6,7-octahydronaphthalene Chemical compound C1CCC2CCCCC2=C1 POPHMOPNVVKGRW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 125000000686 lactone group Chemical group 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
Abstract
A catalyst for preparing decahydronaphthalene by one-step naphthalene hydrogenation and a preparation method thereof belong to the technical field of synthesis of decahydronaphthalene in organic chemical industry, and can solve the problems of complex process flow, high equipment investment, low selectivity of decahydronaphthalene, easy poisoning and inactivation of the catalyst and the like in the traditional process for preparing decahydronaphthalene by naphthalene hydrogenation. In addition, the hydrogenation activity and the sulfur resistance of the catalyst can be effectively improved by carbonizing the active metal sites.
Description
Technical Field
The invention belongs to the technical field of synthesis of decahydronaphthalene in organic chemical engineering, and particularly relates to a catalyst for preparing decahydronaphthalene through one-step hydrogenation of naphthalene and a preparation method thereof.
Background
Coal tar is one of the important byproducts in the coking industry, the yield of the coal tar accounts for about 3% -4% of the charged coal, and the annual yield is over 2000 ten thousand tons at present. Naphthalene is an important raw material in the chemical industry and is mainly obtained by processing and separating coal tar. Naphthalene has a high content in coal tar, which accounts for about 10% of the total content of coal tar, and is one of the main products for processing coal tar. Decahydronaphthalene prepared by hydrogenation of naphthalene is a high-quality high-boiling-point organic solvent, is mainly used for producing polyethylene fibers with ultrahigh relative molecular mass, and is also a promising hydrogen storage medium for fuel cells and automobiles. The decalin market will grow larger and larger as the need for high performance polyethylene fibers and hydrogen storage media increases.
Much research has been carried out abroad on the preparation of decalin by hydrogenation of naphthalene in the beginning of the last century. A small number of enterprises such as DuPont company, Germany Degussa, Pasteur and the like produce decahydronaphthalene products, no decahydronaphthalene production factory exists in China, the domestic requirements all depend on import, and the price is very high.
Through experimental research, the technology for preparing decahydronaphthalene by naphthalene hydrogenation mainly has the following two difficulties: 1. the reaction is a continuous reversible reaction and has intermediate products such as octahydronaphthalene, tetrahydronaphthalene and the like, so that a catalyst is required to have good hydrogenation activity and proper reaction temperature; 2. the raw material naphthalene is mainly derived from coal tar processing and extraction, and the sulfur and nitrogen compound content in crude naphthalene is high, so that the catalyst is required to have anti-poisoning capability.
For the above reasons, the present stage hydrogenation of naphthalene to decahydronaphthalene is usually carried out by using a two-step process. Taking the Chinese patent CN104744203A as an example, Al is adopted in the first step of the patent2O3The loaded transition metal sulfide is used as a catalyst, and the catalyst is used for carrying out hydrodesulfurization and denitrification on naphthalene, so that the catalyst for preparing decahydronaphthalene by naphthalene hydrogenation is prevented from being poisoned and inactivated; and the second step is to further catalyze and synthesize the decahydronaphthalene by the refined naphthalene through a noble metal catalyst with high hydrogenation activity. However, the method has the disadvantages of complex operation, long process flow and high equipment investment.
At the present stage, research related to the preparation of decahydronaphthalene by one-step hydrogenation of naphthalene is carried out. Chinese patent CN1546442A discloses a nickel-based catalyst, which adopts tetrahydronaphthalene as solvent, and has reaction pressure of 6-12MPa and volume space velocity of 0.5-1.0h-1Under the condition of the reaction temperature of 180 ℃ and 220 ℃, the conversion rate of naphthalene reaches more than 98 percent, the side reaction product is lower than 1 percent, but the catalyst of the method has lower reaction activity, and the product decalin has low purity.
Chinese patent CN101602644A discloses a one-step hydrogenation synthesis of naphthaleneA catalyst of decalin and a method thereof. The method adopts Ni/Al2O3Naphthalene is taken as a catalyst and is used as a raw material to synthesize decahydronaphthalene in a reaction kettle by a one-step method. However, the method for preparing decahydronaphthalene in a reaction kettle cannot be used for continuous production and is not suitable for industrial application.
Therefore, the sulfur-tolerant catalyst with ultrahigh hydrogenation activity for preparing the decahydronaphthalene by one-step naphthalene hydrogenation is developed, so that the process flow and equipment investment can be effectively reduced, and the naphthalene conversion rate and the decahydronaphthalene selectivity can be effectively improved.
Disclosure of Invention
The invention provides a novel catalyst for preparing decahydronaphthalene by one-step naphthalene hydrogenation and a preparation method thereof, aiming at the problems of complicated process flow, high equipment investment, low selectivity of decahydronaphthalene, easy poisoning and inactivation of the catalyst and the like in the traditional naphthalene hydrogenation process for preparing decahydronaphthalene. The catalyst reduces unstable groups such as surface carboxyl, phenolic lactone group and the like, reduces surface acid sites, and effectively improves the dispersion degree of metal active components and the selectivity of a product decalin by pretreating a carrier. In addition, the hydrogenation activity and the sulfur resistance of the catalyst can be effectively improved by carbonizing the active metal sites.
The invention adopts the following technical scheme:
a catalyst for preparing decahydronaphthalene by one-step hydrogenation of naphthalene takes activated carbon as a carrier and transition metal as a metal active component, wherein the metal active component comprises a main catalyst and an auxiliary agent, the activated carbon accounts for 55-90% of the mass of the catalyst, and the metal active component accounts for 10-45% of the mass of the catalyst; the main catalyst accounts for 60-85% of the mass of the metal active component, and the auxiliary agent accounts for 15-40% of the mass of the metal active component.
Further, the main catalyst comprises one or two of tungstate and molybdate.
Further, the auxiliary agent comprises one or two of Ni salt and Co salt.
A preparation method of a catalyst for preparing decahydronaphthalene by one-step hydrogenation of naphthalene comprises the following steps:
firstly, preparing a carrier:
(1) dissolving one or more of potassium permanganate, hypochlorous acid, concentrated nitric acid, NaOH and KOH in deionized water to prepare a solution I;
(2) soaking the activated carbon in the solution I for 3-5h, and then putting the solution I into an oven for drying; the volume ratio of the solution I to the activated carbon is more than or equal to 1.5.
(3) Putting the dried activated carbon into a reactor and introducing H2Carrying out reduction pretreatment in the tubular furnace, keeping the temperature at 500-800 ℃ for 1-4h, and obtaining a catalyst carrier after the treatment is finished;
step two, preparing a catalyst:
(1) dissolving the metal active component in deionized water to prepare a solution II;
(2) loading the solution II on a catalyst carrier by adopting an isometric impregnation method to prepare a catalyst precursor;
(3) placing the catalyst precursor in an oven for drying after being placed for 10-24h at normal temperature;
(4) putting the dried catalyst precursor into a reactor filled with N2Roasting in a protected muffle furnace at the temperature of 400-750 ℃ for 2-5h to obtain an oxidation state catalyst;
(5) placing the oxidation state catalyst in a fixed bed, and introducing CH4/H2Keeping the temperature of the mixed gas in the fixed bed at 600-850 ℃ for 1-4h to obtain the carbonized catalyst.
At the temperature of 200 ℃ and 450 ℃, the volume space velocity of the solution of naphthalene/cyclohexane (volume ratio of 1: 10-2: 1) is 0.1-3h-1The catalyst prepared by the method is hydrogenated to prepare the decahydronaphthalene under the process condition that the hydrogen-oil ratio is 10-1000, the conversion rate of the naphthalene is 30-99.5%, and the highest selectivity of the decahydronaphthalene is 98%.
The invention has the following beneficial effects:
the catalyst is a special catalyst for preparing decahydronaphthalene by one-step hydrogenation of naphthalene, which is developed according to the composition and property characteristics of industrial naphthalene extracted from coal tar. The metal hydrogenation active site in the catalyst has good hydrogenation activity on naphthalene and tetrahydronaphthalene, and promotes naphthalene to generate decahydronaphthalene through a hydrogenation path. And the acidic position of the carrier causes the C-C bond of naphthalene and decahydronaphthalene to be broken, ring opening and cracking products are generated, and the selectivity and the yield of decahydronaphthalene are reduced. Therefore, the invention reduces the acidity of the catalyst by modifying the carrier so as to reduce the generation of by-products and improve the dispersion degree of the metal active components. Meanwhile, the hydrogenation activity of the catalyst is improved and the conversion rate of naphthalene is improved by carbonizing and pretreating the metal active components.
Drawings
FIG. 1 is a diagram showing the routes of main reaction and side reaction in the preparation of decalin by hydrogenation of naphthalene.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
7g of potassium permanganate is dissolved in 50ml of deionized water to prepare a solution I, and 10g of active carbon is soaked in the solution I and oxidized for 5 hours. Drying the oxidized active carbon in an oven, placing the dried active carbon in a tubular furnace, and introducing H at 600 DEG C2(50 ml/min) for 2h, and cooling the tubular furnace to normal temperature after the reaction is finished to obtain the catalyst carrier.
And (2) taking nickel nitrate as an auxiliary agent and ammonium metatungstate as a main agent, simultaneously dissolving metal active components in a proper amount of deionized water to prepare a solution II, and uniformly loading the solution II on a catalyst carrier by an isometric impregnation method to obtain a catalyst precursor. And placing the catalyst precursor in an oven for drying after being placed for 24 hours at normal temperature. Putting the dried catalyst precursor into a reactor filled with N2And (3) roasting the catalyst in the protected muffle furnace at 600 ℃ for 3 hours to obtain the oxidation state Ni-W/C catalyst, wherein the mass of Ni and W accounts for 4 percent and 16 percent of the total mass of the catalyst respectively. Finally, the catalyst in the oxidized state is placed in a fixed bed and CH is introduced4/H2Keeping the temperature of the mixed gas in a fixed bed at 700 ℃ for 2h to obtain Ni-W2C/C catalyst.
After the catalyst is prepared, the gas circuit of the fixed bed is switched to H2And adjusting reaction process conditions, wherein the process adjustment specifically comprises the following steps: the reaction temperature is 230 ℃, the volume ratio of naphthalene to cyclohexane is 1: 5, and the space velocity of the solution volume is 0.3h-1And hydrogenating the catalyst prepared by the method under the process condition that the hydrogen-oil ratio is 500 to prepare the decahydronaphthalene. The results of the experiment are shown in table 1.
Example 2
8ml of concentrated nitric acid with the concentration of 60 percent is dissolved in 50ml of deionized water to prepare solution I, and 10g of activated carbon is soaked in the solution I to be oxidized for 5 hours. Drying the oxidized active carbon in an oven, placing the dried active carbon in a tubular furnace, and introducing H at 700 DEG C2(60 ml/min) for 3h, and cooling the tubular furnace to normal temperature after the reaction is finished to obtain the catalyst carrier.
And (2) taking cobalt nitrate as an auxiliary agent and ammonium metatungstate as a main agent, simultaneously dissolving the metal active components in a proper amount of deionized water to prepare a solution II, and uniformly loading the solution II on a catalyst carrier by an isometric impregnation method to obtain a catalyst precursor. And placing the catalyst precursor in an oven for drying after placing the catalyst precursor for 18h at normal temperature. Putting the dried catalyst precursor into a reactor filled with N2And (3) roasting the catalyst in a protected muffle furnace at 700 ℃ for 3 hours to obtain an oxidation state Co-W/C catalyst, wherein the mass of Co and W accounts for 2 percent and 13 percent of the total mass of the catalyst respectively. Finally, the catalyst in the oxidized state is placed in a fixed bed and CH is introduced4/H2Keeping the temperature in the fixed bed for 2h at 750 ℃ to obtain Co-W2C/C catalyst.
After the catalyst is prepared, the gas circuit of the fixed bed is switched to H2And adjusting reaction process conditions, wherein the process adjustment specifically comprises the following steps: the reaction temperature is 280 ℃, the volume ratio of naphthalene to cyclohexane is 1: 3, and the volume space velocity of the solution is 0.2h-1And hydrogenating the catalyst prepared by the method under the process condition that the hydrogen-oil ratio is 800 to prepare the decahydronaphthalene. The results of the experiment are shown in table 1.
Example 3
10g of NaOH is dissolved in 50ml of deionized water to prepare a solution I, and 10g of activated carbon is soaked in the solution I and oxidized for 5 hours. Drying the oxidized active carbon in an oven, placing the dried active carbon in a tubular furnace, and introducing H at 750 DEG C2(800 ml/min) for 4h, and cooling the tubular furnace to normal temperature after the reaction is finished to obtain the catalyst carrier.
And (2) taking cobalt nitrate as an auxiliary agent and ammonium molybdate as a main agent, simultaneously dissolving the metal active component in a proper amount of deionized water to prepare a solution II, and uniformly loading the solution II on a catalyst carrier by an isometric impregnation method to obtain a catalyst precursor. Will be hastenedThe precursor of the agent is placed in an oven for drying after being placed for 12 hours at normal temperature. Putting the dried catalyst precursor into a reactor filled with N2And (3) roasting the catalyst in a protected muffle furnace at 650 ℃ for 4 hours to obtain an oxidation state Co-Mo/C catalyst, wherein the mass of Co and Mo accounts for 3 percent and 18 percent of the total mass of the catalyst respectively. Finally, the catalyst in the oxidized state is placed in a fixed bed and CH is introduced4/H2Keeping the temperature in the fixed bed for 2h at 780 ℃ by using mixed gas to obtain Co-Mo2C/C catalyst.
After the catalyst is prepared, the gas circuit of the fixed bed is switched to H2And adjusting reaction process conditions, wherein the process adjustment specifically comprises the following steps: the reaction temperature is 300 ℃, the volume ratio of naphthalene to cyclohexane is 1: 5, and the space velocity of the solution volume is 0.5h-1And hydrogenating the catalyst prepared by the method under the process condition that the hydrogen-oil ratio is 900 to prepare the decahydronaphthalene. The results of the experiment are shown in table 1.
Example 4
The hypochlorous acid with the concentration of 20 percent is dissolved in 40ml of deionized water to prepare a solution I, and 10g of active carbon is soaked in the solution I to be oxidized for 3 hours. Drying the oxidized active carbon in an oven, placing the dried active carbon in a tubular furnace, and introducing H at 800 DEG C2(800 ml/min) for 3h, and cooling the tubular furnace to normal temperature after the reaction is finished to obtain the catalyst carrier.
And (2) taking nickel nitrate and cobalt nitrate as auxiliary agents, taking ammonium metatungstate and ammonium molybdate as main agents, simultaneously dissolving metal active components in a proper amount of deionized water to prepare a solution II, and uniformly loading the solution II on a catalyst carrier by an isometric impregnation method to obtain a catalyst precursor. And placing the catalyst precursor in an oven for drying after 12 hours at normal temperature. Putting the dried catalyst precursor into a reactor filled with N2And (3) roasting the catalyst in a protected muffle furnace at 700 ℃ for 4 hours to obtain the oxidation state Ni-Co-W-Mo/C catalyst, wherein the mass percentages of Ni, Co, W and Mo in the catalyst in the total mass are respectively controlled to be 1.2%, 1.7%, 10% and 8%. Finally, the catalyst in the oxidized state is placed in a fixed bed and CH is introduced4/H2Keeping the temperature in the fixed bed for 2h at 780 ℃ to obtain Co-Ni-W2C-Mo2C/C catalyst.
After the catalyst is prepared, the gas circuit of the fixed bed is switched to H2And adjusting reaction process conditions, wherein the process adjustment specifically comprises the following steps: the reaction temperature is 350 ℃, the volume ratio of naphthalene to cyclohexane is 1: 10, and the volume space velocity of the solution is 0.8h-1And hydrogenating the catalyst prepared by the method under the process condition that the hydrogen-oil ratio is 1000 to prepare the decahydronaphthalene. The results of the experiment are shown in table 1.
Comparative example 1
The non-pretreated activated carbon was used as a catalyst carrier, and the rest of the preparation method and reaction process of the catalyst were adjusted to the same as in example 1. The results of the experiment are shown in table 1.
Comparative example 2
The pretreatment method of activated carbon, the oxidation state catalyst and the reaction process conditions were the same as in example 2, and the preparation method of the catalyst was changed from carbonization pretreatment to vulcanization pretreatment. Carrying out sulfurization pretreatment on an oxidation state Co-W/C (Co =2%, W = 13%) catalyst, specifically putting the oxidation state catalyst in a fixed bed, and introducing H2S/H2Keeping the temperature in the fixed bed for 5 hours at 400 ℃ to obtain Co-WS2a/C catalyst. The results of the experiment are shown in table 1.
TABLE 1 results of the experiment
As can be seen from examples 1-3 and example 4, the synergistic effect of the active components in the composition is helpful to improve the hydrogenation activity of naphthalene. As can be seen from examples 1-4 and comparative example 1, the pretreatment of the activated carbon can effectively reduce the acid sites on the surface of the catalyst, thereby improving the selectivity of decalin. Meanwhile, unstable groups on the surface of the carrier are removed, which is beneficial to improving the dispersion degree of the metal active components of the catalyst, thereby improving the conversion rate of naphthalene. It can be seen from examples 1-4 and comparative example 2 that the hydrogenation activity of the carbonized catalyst is much higher than that of the sulfided catalyst. In addition, the desulfurization capacity of the carbonized-state catalyst is also higher than that of the vulcanized-state catalyst.
Claims (4)
1. A catalyst for preparing decahydronaphthalene by one-step hydrogenation of naphthalene is characterized in that: the catalyst takes activated carbon as a carrier and transition metal as a metal active component, and the metal active component comprises a main catalyst and an auxiliary agent, wherein the activated carbon accounts for 55-90% of the mass of the catalyst, and the metal active component accounts for 10-45% of the mass of the catalyst; the main catalyst accounts for 60-85% of the mass of the metal active component, and the auxiliary agent accounts for 15-40% of the mass of the metal active component.
2. The catalyst for preparing decalin by one-step hydrogenation of naphthalene according to claim 1, wherein: the main catalyst comprises one or two of tungstate and molybdate.
3. The catalyst for preparing decalin by one-step hydrogenation of naphthalene according to claim 1, wherein: the auxiliary agent comprises one or two of Ni salt and Co salt.
4. A method for preparing the catalyst for one-step hydrogenation of naphthalene to decahydronaphthalene according to any one of claims 1 to 3, which comprises the following steps: the method comprises the following steps:
firstly, preparing a carrier:
(1) dissolving one or more of potassium permanganate, hypochlorous acid, concentrated nitric acid, NaOH and KOH in deionized water to prepare a solution I;
(2) soaking the activated carbon in the solution I for 3-5h, and then putting the solution I into an oven for drying; the volume ratio of the solution I to the activated carbon is more than or equal to 1.5;
(3) putting the dried activated carbon into a reactor and introducing H2Carrying out reduction pretreatment in the tubular furnace, keeping the temperature at 500-800 ℃ for 1-4h, and obtaining a catalyst carrier after the treatment is finished;
step two, preparing a catalyst:
(1) dissolving the metal active component in deionized water to prepare a solution II;
(2) loading the solution II on a catalyst carrier by adopting an isometric impregnation method to prepare a catalyst precursor;
(3) placing the catalyst precursor in an oven for drying after being placed for 10-24h at normal temperature;
(4) putting the dried catalyst precursor into a reactor filled with N2Roasting in a protected muffle furnace at the temperature of 400-750 ℃ for 2-5h to obtain an oxidation state catalyst;
(5) placing the oxidation state catalyst in a fixed bed, and introducing CH4/H2Keeping the temperature of the mixed gas in the fixed bed at 600-850 ℃ for 1-4h to obtain the carbonized catalyst.
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| CN202111483577.9A CN114011428B (en) | 2021-12-07 | Catalyst for preparing decalin by naphthalene one-step hydrogenation and preparation method thereof |
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